Process of treating hydrocarbons with alpha chlorinated hydrocarbon in the presence of alpha metallic halide



Sept. 20, 1932. l M, CHAPPELL 1,878,262

PROCESS 0F TREATING HYDROCARBONS WITH A CHLOHINATED HYDROCARBON IN THEPRESENCE OF A METALLIC HALIDE Original Filed Jan. 22. 1927 PatentedSept. 20, 1932 UNITED STATES MARVIN L. CHAPPELL, OF LOS ANGELES,CALIFORNIA, ASSIGNOR TO STANDARD OIL COMPANY OF CALIFORNIA, OF SANFRANCISCO, CALIFOIR/NLL A CORPORATION OF DELAWARE I PROCESS 0F TREATINGHYDROCARBONS WITH A. GHLORINATED` HYDROCARBON 1N THE PRESENCE OF AMETALLIC HALIDE Application led January 22, 1927, Serial No. 162,752.Renewed August 21, 1981.

This invention relates to the treatment of hydrocarbon oils, and is ofparticular 'value for the treatment of hydrocarbon oils high incarboeyclic compounds such as petroleumv oils found in California,Texas, Mexico, Russia, and other places; or oils derived by thedistillation of any petroleum hydrocarbon of the carbocyclic series,which may be shale oils or coal tar oils, with a metallic halide such asaluminum-chloride, iron chloride, and the like, in the anhydrous form,and refers particularly to a continuous, batch, or intermittent processof treating hydrocarbon oil With a metallic halide of which aluminumchloride is preferred, in the presence of a chlorinated hydrocarbon gasof the paraliin series.

It is well known in the science of chemistry that a chlorinatedhydrocarbon, such as methyl or ethyl chloride will react with an oil ofthe aromatic series to produce a methyl or ethyl aromatic oil, such asmethyl benzol and the like; this reaction being known as theFriedel-Crafts synthesis to which reference is hereby made to Weyl, DieMethoden der organischen Chemie, Volume l, page 297.

' I have discoveredv that this reaction may also be applied to thepetroleum oils, particularly those containing, oils of the carbocyclicseries, preferably a distillate, which will react witha chlorinated gasof the aliphatic series,- in the presence of aluminum chloride at atemperature of approximately 212 F. Such carbocyclic oils may be of thenaphthenic type or other similar types of the carbocyclic series. Thereaction between the said carbocyclic oils and the said chlorinatedhydrocarbon gas results in the condensation of the hydrocarbon radicalof the chlorinated gas and the carbocyclic oil with the evolution ofHC1. The following represents the type of reaction which takes place, inwhich the CH3- radical may be any other radical of the aliphatic seriessuch as C2115, CSH? and the like, and the R radical represents anyhydrocarbon with a ring structure such as a naphthene, a polynaphthene,aromatic oils, etc.:

CHSCHRH A1013 011,11 +HC1+A1C13- I have further discovered that thiscondensed hydrocarbon produced by the action of a carbocyclic oil and achlorinated hydrocarbon in the presence of aluminum chloride at atemperature of approximately 212 F. may be further reacted upon by afurther addition of aluminum chloride at a temperature ranging from 300F. to 650 F. to form gasoline or naphtha and a higher boiling oil.

An obj ect of thepresent invention is to provide a process for treatinghydrocarbon oil, preferably distillate, with` aluminum chloride in whichthe said hydrocarbon oil and aluminum chloride are agitated together bymeans of a chlorinated hydrocarbon gas ofthe aliphatic series at atemperatu-re suflicient to cause a chemical reaction therein with Itheevolution of HCl and the formation of a condensed oil; transferring saidcondensed oil to a second reaction chamber and mixing therewith afurther addition of aluminum chloride, maintaining in said secondreaction chamber a temperature greater than 300 F., 'commlngling thesaid polymerized oil and aluminum chloride for a suicient period of Ytime and at a sufcient temperature to cause a reaction therein with theproduction of na htha or gasoline and a higher boiling hy rocarbon oil.

Another object of the present invention is to provide a continuous orintermittent process for treating hydrocarbon oils of the carbocyclicseries with aluminum chloride in the presence of a chlorinatedhydrocarbon gas to produce therein a condensation ofthe said carbocyclicoil and the hydrocarbon radical of the chlorinated gas for a. stocksuitable for the manufacture of lubricating oil.

Another object of the invention is to produce a gasoline or motor fueland a stock suitable for the manufacture of lubricating oil from a highboiling hydrocarbon oil ofthe carbocylic series and a hydrocarbon gasderivedfrom oil wells or natural methane lUU ' upon the ride underatmospheric or superatmospheric condition for the production of gasolineor motor fuel and a higher boiling oil suitable for the production of alubricating oil stock.

Another object of the invention is to provide a process in which the,unconverted chlorinated hydrocarbons may be separated from the HC1produced by the reaction and returned to the system.

In accordance with the process of the present invention hydrocarbongases, preferably those derived from oil wells or natural gas wells, arechlorinated by well known methods, for example by the addition of orcontact with chlorine gas alone or in the presence of chlorides, andthen introduced into a body of high boiling hydrocarbon oils, preferablycontaining a large amount of hydrocarbons of the carbocyclic series towhich has been added a metallic halide, preferably aluminum chloride, inamounts ranging from l to as high as SU ounds per gallon of high boilinghydrocar on oil. This mixture is maintained at the reaction temperaturesuitable for condensation of said constituents as heretofore stated, theoil being continuously agitated by means of a continuous introduction ofthe said chlorinated gas. The products of reaction consisting of thecondensed oil and the hydrocarbon radical of the said 4chlorinated gasare continuously or intermittently pumped to a second reaction chamber.The evolved gases consisting of HCl and the chlorinated gas are pumpedinto a fractionating column at a sulicient pressure and reduced to asuiiiciently low temperature so that the chlorinated hydrocarbon willliquefy and may be drawn oif from the bottom 0f the fractionating systemand returned to the system. The HC1 is evolved from the top of saidfractionating system and may be converted to chlorine gas by well knownprocesses such as the Deacon. The condensed hydrocarbon oil which may becontinuously or intermittently introduced into the second reactionchamber is agitated with a further addition of aluminum chloride whichmay range from $6 to as high as 3/4, of a pound of anhydrous aluminumchloride per gallon of oil introduced. In said reaction chamber, thetemperature ranging from 300 F. to as high as 650 F. is maintained,depending roducts desired and the product treated. n case a small amountof gasoline is desired and a larger amount of lubricating stock, asmaller amount of aluminum chloride is introduced into said reactionchamber. This said reaction chamber for the production of gasoline froma condensed oil, is preferably carried at a pressure of approximately 15pounds gauge, and the gasoline produced therein together with higherboiling hydrocarbons are vaporized and carried into a dephlegmatingtower provided with a cooling medium or planer at the top,

where said higher boiling hydrocarbons are condensed and return to thereiiuX line. The reiuxed oil may be used for the manufacture of alubricating oil stock or may be returned to the reaction chamber forfurther reaction with aluminum chloride, or said refluxed oil afterbeing returned to the reaction chamber together with the aluminumchloride may be introduced into a still and therein vaporized for theremoval of all carbonaceous material and then returned again to thereaction chamber for further action with aluminum chloride for theproduction of gasoline.

The reaction between the condensed hydrocarbon oil and the aluminumchloride in the reaction chamber provided with a mechanical stirrer maybe modified for the production of the desired products by regulating theheat and pressure and quantity of metallic halide employed. For example,if it is desired to obtain a gasoline or naphtha having a highpercentage of low boiling hydrocarbon oils, a higher pressure andtemperature is maintained in the reaction chamber than would be employedfor the production of a higher boil- The process of the presentinvention is preferably continuous but may be operated intermittently orin batch lots.

Various further objects and advantages of the present invention will beunderstood from a description of the preferred process of treating ahydrocarbon oil in the presence of a chlorinated hydrocarbon gasemploying the present invention. For this purpose, there is hereafterset forth a specific example of one form of process which embodies theinvention. The process is described as it is carried out in theapparatus illustrated in the accompanying drawing. h

The drawing represents a diagrammatic elevation in vertical section ofthe complete apparatus. V

Referring to the drawing, 1 indicates genp erally a reaction chamberwhich is preferably mounted over a suitable heating means, such as thefurnace 3 having the burner 4. The reaction chamber 1 is also provided.with a charger 21 for introducing aluminum chloride into the lreactionchamber, said charger 21 including a hopper 26, two spaced valves 22 and25, a line 24 controlled by a valve 23, line 24 leading to a source ofaluminum chloride, not shown, for the introduction of aluminum chloridein a liquid or dissolved state, controlled by said valve 23.

The reaction chamber 1 is also preferably provided with an oil chargingline V19 and a residual draw-olf line 2 7 with a branch line 28controlled by a valve 29. The branch line 28 leads to a tank 33. Thetank 33 is provided with a. draw-off line 34 controlled by a valve 35.The draw-of line 27 leads to the suction side ofa pump 30 and dischargesinto a line 31 which is connected to a second reaction chamber 32provided with a mechanical stirrer 36. The mechanical stirrer 36 isprovided with paddles 37 so that the products undergoing reaction may bekept in a constant agitation.

The reaction chamber 1 is provided on the top with a dome 7 which isconnected to a line 10 leading to the suction sidek of pump 9, whichdischarges into line 10. The line 10 is connected to a dephlegmator 11which is provided with a planer or condenser 12. 13 is a line whichleads to a source of cooling medium, such as liquefied ammonia, or otherfluids for obtaining very low temperatures, not shown, and 14 is a lineleading from the condenser or planer 12 to carry olfthe supply ofcooling medium introduced. 15 is a line connected to the top of thedephlegmator 11 controlled by pressure regulating valve 16 and leadingto a source, not shown, for conducting the HC1 formed in the process toa suitable apparatus for the production of chlorine, such as the Deaconprocess. The dephlegmator 11 is connected at the bottom by a line 17,controlled by a valve 18, and also connected .to the line 2 which isused for conducting the condensed liquefied, chlorinated hydrocarboninto the'line 2vwhich enters reaction chamber 1 along the bottomcontrolled by valve 5. The line 2 leads to a source of chlorinatedhydrocarbon of the paraffin series, not shown, and enters the reactionchamber 1, as heretofore stated, along the bottom and containsperforations, as indicated at 6, so that the introduced chlorinatedgases may agitate the admixture within the reaction chamber 1. y

The second reaction chamber 32, into which the condensed oils areconducted from the reaction chamber 1, is provided with a charger 40 forintroducing aluminum chloride into the reaction chamber, said charger 40including a hopper 45, two space valves 43 and 44, a line 42 controlledby a Valve 41, line 42 leading to a source of aluminum chloride, notshown, for the introduction of aluminum chloride in a liquid or`dissolved state.

The reaction chamber 32 is also provided with a dome 46 on the top towhich is connected a line 47 leading to a dephlegmator 48. Interposed inthe top of said dephlegmator 48 is a planer or condenser 49 connected toa line 51 which leads to a source of water or other liquid coolingmedium, not shown. A line 52 is connected to said condenser or planer 49for 'conducting away the cooling medium toa place not shown. Connectedat the top of said dephlegmator 48 is a line 53 leading to a condenser54, interposed in a condenser box 55, where the gasoline vapors arecondensed to a liquid and passed through line 56 into the gasolinereceiving tank 57. Gasoline receiving tank 57 contains a line 59 in thetop and a valve 58 to regulate the pressure on the system.

Connected at the bottom of said dephlegmator 48 is a drain line 80controlled by a valve 81, which line 80 leads to a tank A62. Said tank62 is provided with a draw-oil' line at the bottom 63, controlled by avalve 64.

The draw-olf line 80 which leads from the' Connected at the bottom ofthe reaction' chamber 32 is a line 66 controlled by a valve 65 whichleads to the suction side of a pump 67, which discharges into the line82. The` line 82 is connected to a still 68 at the top, so

that the products of reaction from the reaction chamber 32 may beintroduced intol said still and there converted into vapors which passthrough the dome 69 interposed upon the top of`said still 68, into aline 70 and from there into the dephlegmator 48.

The still 68 is mountedover a furnace 71 provided with a burner 72. Thesaid still 68 is also provided with a man-hole 73 at the bottom, so thatthe coke accumulating from any distillation may be removed.

The preferred process as carried out with the apparatus thus describedis as follo s Hydrocarbon oil, preferably one contai y considerablehydrocarbons of the carbccyclic Series, is introduced intoreactionchamber 1, preferably continuously, and a chlorinated hydrocarbon gas,preferably mainly of the paraliin series, is introduced continuouslythrough the line 2, entering the reaction chamber 1 through theperforations in said pipe, thereby agitating and producing an intimatecontact between the oil and gas. Preferably the chlorinated hydrocarbongas is obtained by chlorinating natural gas. Thereis also preferablycontinuously introduced through the charger 21, aluminum chloride at'the rate of .1 to as high as .5 pound.

erably approximately 212 F. is maintained in the reaction chamber 1 andcauses a portion of the chlorinated hydrocarbon gas to react with thehydrocarbon oil (principally the carbocyclic oil) While HC1 is evolved.The hydrogen chloride gas HC1 passes upwardly through dome 7 into line 8and into pump 9 along with that part of the chlorinated hydrocarbonwhich did not combine. The said HC1 and chlorinated hydrocarbon gas arecompressed by means of the pump 9 and enter the dephlegmator 11 Wherethey are cooled to such a temperature that the unacted upon chlorinatedhydrocarbon gas is condensed to a liquid and is returned to the reactionchamber through the bottom of the dephlegmator 11 into pipe' 17 and backto the reaction chamber 1. The HCl gas, on account of its very lowboiling point, isnot liquefied and is therefore separated from thechlorinated hydrocarbon and is drawn off from the dephlegmator 11 at thetop through the line 15 controlled by the pressure regulatinrr valve 16and then conducted to a place, not s iown, for the manufacture ofchlorine as. g The hydrocarbon oil after being reacted upon asheretofore stated by the chlorinated hydrocarbon gas With the formationof condensed products, is continuously drawn olf through the line 27into the suction side of a pump 30 which discharges into a secondreaction chamber 32 through the line 31, or in case it is desired tomake a, lubricating oil stock, the condensed oil coming from reactionchamber lis run through line 28 into the tank 33 and thereaftermanufactured into high grade lubricating oil by processes Well known.This condensed oil may also be employed as a charging stock of a thermalcracking process.

In case, however, it is desired toconvert a part or all of the condensedstock coming from reaction chamber 1 into gasoline or motor fuel, saidpump 30 discharges the condensed product into the reaction chamber 32.Aluminum chloride, in portions varying from as low as .2 to as high as1% of a pound per gallon of oil charged into the reaction chamber 32, isintroduced through the charger 40, either in the form of a solid or in adissolved solution. The reaction chamber 32 is carried at al temperatureranging from 300 to as high as 650 F., and preferably under a pressureof approximately 15 pounds gage, depending upon the product treated andthe products desired. In case a high percentage of loW boilinghydrocarbons is desired a higher temperature and a higher pressure areemployed. -The converted oil in the aluminum chloride passes through theline 47 into the dephlegmator 48 Where the aluminum chloride and higherboiling hydrocarbons are ocondensed and may be returned to the systemthrough the line 8O and then into the line 61, valve 81 being closed,and valve 60 open. In case it is desired to produce a small amount ofhigher boiling stock suitable for the manufacture of lubricating oil orother purposes, the said reliux coming from the dephlegmator 48 ispermitted to'pass down the line 80 and into the tank 62, valve 81 beingopenand valve closed.

The gasoline or motor fuel produced by the action of aluminum' chloridein reaction chamber 32, after passing through the dephlegmator 48,passes into the line 53 from the top of said dephlegmator 48 and theninto the condenser 54 Where said low boiling hydrocarbons or gasolinestock is condensed and passed into the gasoline receiving tank 57, thepressure on the system being controlled by the valve 58, which isconnected into the.

line 59.

The aluminum chloride residuum along with some ofthe higher boilinghydrocarbon oil lare continuously withdrawn from thereaction chamber 32through line 66 controlled by valve into the suction side of the pump67, which discharges into the line 82 connected to the still 68 at thetop, so thatrwhen it is desired to obtain as high a yield as poscible ofstock suitable for motor spirits or gasoline, thel reflux fromdephlegmator 48 is permitted to flow back through pipe 80 into line 61and thereafter into the reaction chamber 32 where it is again reactedupon by the aluminum chloride. By means of this still 68, thecarbonaceous matter resulting from the aluminum chloride reaction may becontinuously removed from the hydrocarbon oils as produced.

The chlorinated hydrocarbon gas employed in this process may be anychlorinated hydrocarbon of the aliphatic or paraiin series such, forexample as methane, ethane, butane, pentane etc., of the general formulaCnHgm, and the high boiling hydrocarbon, any oil containing compounds ofthe carbocyclic series, such as naphthanes, polynaphthenes, aromaticoils, etc., represented by the formulas CnH2n9 CnH2n-2, CnH2n-4, andCnHZn-G- HOW' ever, it is to be understood that the high boilingpetroleum oils may be one of the mixed base type, by which is meant anaphthenic oil containlng as much as 50 per cent. of hydrocarbons of thealiphatic or other series. In the second step of the process Where theoils are again reacted upon by a further addition of aluminum chlorideat higher temperatures for the decomposing reaction and the formation ofgasoline, 'the aluminum chloride not only decomposes the condensed oilbut also the other oils of any other series that may be present therein.

It is also to be understood that the condensation reaction between thechlorinated gas and the hydrocarbon oil or its content o f carbocyclicoil may not be quantitive,"

smce, 1n some cases, as low as 10 per cent of the carbocyclic oil may beonly reacted upon by the chlorinated gas, and in other cases as high as98 per cent.

An important feature of the present process is the production ofgasoline or lubricating oils using in part fixed gases such as methane,which hitherto have not been utilized for that purpose.

While the process herein described is well adapted for carrying out theobjects of the present invention, it is understood that variousmodifications may be made without departing from the invention and theinvention includes all such modifications and changes as come within thescope of the appended claims.

I claim:

1. A methodv of treating hydrocarbon oil containing hydrocarbons rof thenaphthenic type which comprises treating said oils with a chlorinatedgas of the aliphatic series in the presence of a metallic halide attemperatures suitable for the production of a condensation reactiontherein between the hydrocarbons of the naphthenic type and thechlorinated hydrocarbon, introducing a further amount of metallic halideraising the temperature sufficiently to produce a decomposing reactionbetween said metallic halide and 011s for the production of gasoline,withdrawing metallic halide residue into ,a still, separating saidmetallic halide residue and tarry constituents by a distillationoperation, returnin the high boiling oil distilled therefrom ack to thereaction chamber to be further reacted upon by metallic halide for thefurther production of gasoline.

2. A method of treating hydrocarbon oil containing hydrocarbons of thenaphthenic type which comprises treating said oils with a chlorinatedgas of the aliphatic series in the presence of a metallic halide attemperatures suitable for the production of a condensation reactiontherein between the hydrocarbons of the naphthenic type and thechlorinated hydrocarbon in a reaction zone, withdrawing said condensedoil together with the unacted upon oil into a second reaction zone,introducing a further amount of metallic halide into said reaction zoneand raising the temperature suiiiciently therein to produce adecomposing reaction between said metallic halide and oils for theproduction of gasoline and a high boiling oil, withdrawing said highboiling oils and metallic halide residue into' a still, separating saidmetallic halide residue and tarry constituents by a distillationoperation, returning the higher boiling oils to a separate condenser tobe utilized for the manufacture of lubricating oil stock.

3. A method of treating hydrocarbon oil containing hydrocarbons ofthenaphthenic type which comprises treating 4said oil with a chlorinatedgas of the aliphatic series in the presence of aluminum chloride attemperatures suitable for the production of a condensation reactiontherein between the hydrocarbon of the naphthenic type and thechlorinated hydrocarbon, introducing a further amount of aluminumchloride, raising the temperature sufliciently to produce a decomposingreaction between said aluminum chloride and oils for the production ofgasoline, withdrawing the aluminum chloride residue into a distillationzone, separating said aluminum chloride residue and tarry constituentsby a distillation operation in such zone, and returning the high boilingoil distilled therefrom back to the reaction chamber to be furtherreacted upon by aluminum chloride for the further production ofgasoline.

4. In a method of treating hydrocarbon oils, the steps of forming amixture of hydrocarbon oil containing hydrocarbons of naphthenic typewith a metallic halide in a reaction zone, passing a stream ofchlorinated light aliphatic paraiins into the oil--halide mixtureundergoing reaction in a reaction zone, whereby condensation and.polymerization reactions result therein between the hydrocarbons of thenaphthenic type and the chlorinated hydrocarbons, vaporizing from suchmixture hydrogen chloride and that part ofthe chlorinated paraiins whichdo not react in said reaction zone, separating said unacted uponchlorinated paraiiins from said hydrogen chloride, returning saidseparated unacted upon chlorinated paraflins to the reaction zone, andseparately removing polymerized and condensed hydrocarbon oil from said'reaction zone.

`5. A method of treating hydrocarbon oil containing hydrocarbons of thenaphthenic type, which comprises treating said oil with a gas containingchlorinated hydrocarbons of the aliphatic series in the presence ofaluminum chloride at temperatures suitable for the production of acondensation reaction therein between the hydrocarbon of the naphthenict pe and the chlorinated hydrocarbons, introucing a furtherA amount ofalumlnum chloride, raising the temperature suiiiciently to produce adecomposing reaction between said aluminum chloride and oils for theproduction of gasoline, withdrawing the aluminum chloride residue'into adistillation zone, and separating said aluminum chloride residue andtarry constituents by a distillation operation in such zone.

6. In a method of treatinghydrocarbon oils, the steps of forming amixture of hydronaphthenic type with a metallic halide in a reactionzone, passing a stream of hydrocarbon oil well gases containingchlorinated light aliphatic paratlins into the oil-hallde 1,25 i carbonoils containing hydrocarbons of the mixture undergoing reaction in areaction zone, whereby condensation and polymerization reactions result'therein between the hydrocarbons of the naphthenic type and thechlorinated hydrocarbons, vaporizing from such mixture hydrogen chlorideand that part of the chlorinated paraius which do not react in saidreaction zone, separating said unacted upon chlorinated parailins fromsaid 10 hydrogen chloride, and separately removing polymerized a'ndcondensed hydrocarbon oil from said reaction zone. A

7. A method of treating hydrocarbon oils containing hydrocarbons of thenaphthenic type, which com rises treating said oils with a hydrocarbon011 well gas containing chlorinated hydrocarbons of the aliphatic seriesin the presence of aluminum chloride at temperatures suitable for theproduction of a condensation reaction therein between the hydrocarbonsof the naphthenic type and the chlorinated hydrocarbon in a reactionzone, withdrawing said condensed oil together with the una'cted upon oilinto a second reaction zone, introducing a further amount of aluminumchloride into said reaction zone, raising the .temperature sufiicientlytherein to pro-- duce a decomposing reaction between saidv aluminumchloride and oil for the production of gasoline and a high boiling oil,withdrawing said high boiling oil and aluminum chloride residue into astill, and separating said aluminum chloride residue and tarryconstituents by a distillation operation.

85 8. A method of treating hydrocarbon oils 'containing hydrocarbons ofthe naphthenic type, which com rises treating said oils with ahydrocarbon o1l well gas containing chlorinated hydrocarbons of thealiphatic series in 40 the presence of aluminum chloride at temperaturessuitable for the production of a condensation reaction therein betweenthe h drocarbons of the naphthenic type and t e chlorinated hydrocarbonin a reaction zone,

withdrawing said condensed oil together with the unacted upon oil into asecond reaction zone, introducing a further amount of aluminum chlorideinto said reaction zone, raising the temperature suiiiciently therein toproduce a decomposing reaction between said aluminum chloride and oilfor the production of gasoline and a high boiling oil, discharg`. inggasoline vapors from said reaction zone, and separately discharging saidhigh boiling `55 oil and aluminum chloride yresidue from said reactionzone.

Signed at Los Angeles, Calif.,- this' day of January 1927 MARVIN L.CHAPPELL.

